A popular way of conferring an oil-repellent and/or water-repellent finish on textile material is to use fluorocarbon polymers which provide a certain air and vapour permeability and also an easy care finish, to produce, for example, breathable finishes which are impermeable to water. For general use it is desirable for the finish to have certain fastnesses, particularly cleaning fastnesses, among which the fastness to washing, especially the permanence to washing, plays a particular role; a problem in this is that an impairment of the oleophobic and/or hydrophobic effect of the finish due to a clean with customary household detergents (by washing or shampooing, for example) requires a thermal after treatment, for example at 140xc2x0 C. or higher (by ironing, for example), to be at least partially recoveredxe2x80x94provided there is still product on the substrate after the clean. It is therefore especially desirable for the original properties (particularly the oil- and water-repellent properties and the vapour permeability or the easy care properties) to be essentially intact after one or more cleaning or washing operations, even without a thermal aftertreatment, if possible.
DE 19615116 A1 describes blocked polyisocyanates as crosslinker resins for organic polyhydroxy compounds for clearcoating baking finishes, these blocked polyisocyanates being prepared by reacting an isocyanurate-group-containing (cyclo)aliphatic polyisocyanate with a nonionic hydrophilic component (a Carbowax, for example), a monofunctional blocking agent and a hydrazide-group- containing stabilizing component and optionally certain chain extenders in a certain quantitative ratio, by first reacting the starting polyisocyanate in a non-exhaustive manner with the hydrophilic component and then with the blocking agent and thereafter reacting with the stabilizer and optionally with the chain extender.
EP 0537578 A2 describes the use, together with fluorochemicals, of blocked polyisocyanates which contain polyalkylene ether and have built-in ionic groups for the hydrophobicizing and oleophobicizing finishing of textiles. Such ionically modified products have the disadvantage that they are not necessarily compatible with other products of opposite ionicity, for example anionically modified products and synthetic resin components having a cationic character, since this can lead to precipitates in an aqueous medium.
Later U.S. Pat. No. 5,714,082 describes water- and oil-repellent, soil-repellent finishes with fluoro-chemicals, the use of an extender of the hydrocarbon urethane type (there the nonionic product HCT-3) in Example 42 thereof being designated as contributing to xe2x80x9cdeficienciesxe2x80x9d.
It has now been found that using the hereinbelow defined mixtures (G) of blocked oligomeric isocyanates surprisingly makes it possible to improve the oil- and water-repellent properties and also the fastnesses of the finishes mentioned at the outset.
The invention relates to the defined mixtures (G), compositions comprising these mixtures, the production of the mixtures and their use.
In a first aspect, the invention accordingly provides self-dispersible mixtures (G) of oligomeric isocyanates (C) reacted in part with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, and optionally with a chain extender (K) and exhaustively blocked with an isocyanate-blocking pyrazole (B).
The self-dispersible mixtures (G) can be formulated with water and optionally further additives to form aqueous dispersions (D).
The process for the production of the self-dispersible mixtures (G) is especially characterized in that
in a first process step
(a) a minor proportion of the isocyanate groups in the oligomeric isocyanate (C) are reacted in the absence of protogenic solvents with polyethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, to form a product (U1) and this product (U1) is then optionally converted into a product (U2) which has a higher NCO-based equivalent weight and which still contains reactive NCO groups,
and in a second process step
(b) the remaining isocyanate groups are exhaustively blocked with isocyanate-blocking pyrazole (B).
For the production of the aqueous dispersions (D), the mixtures (G) thus produced can, preferably directly after their production, be mixed with water and optionally further additives.
As oligomeric isocyanates (C) are suitable generally known isocyanates, advantageously having two to ten NCO groups, for example hydrocarbon oligoisocyanates or oligomers of hydrocarbon diisocyanates, especially
(C1) oligomers of aliphatic diisocyanates or
(C2) diphenylmethane diisocyanate or polyphenylenepolymethylene polyisocyanates.
The monomeric aliphatic diisocyanates from which the oligomers (C1) derive preferably have at least one isocyanate group bonded to a methylene. The oligomeric isocyanates (C1) can be for example di-, tri- or tetramers of aliphatic, optionally cyclic diisocyanates having for example 2 to 16, preferably 4 to 10, carbon atoms in the basic hydrocarbon skeleton. Of these, hexamethylene diisocyanate, isophorone diisocyanate and 2,4,4-trimethylhexylene-1,6-diisocyanate are preferred, especially hexamethylene diisocyanate. The oligomers can be cyclic or open-chain; suitable trimers include in particular those having an isocyanurate or biuret structure, while suitable dimers include especially those having a uretidione structure; optionally it is also possible to use oligomers thereof.
The ether-forming alkyl radicals in (A) are in principle discretionary, but are preferably of low molecular weight; they preferably contain 1 to 4 carbon atoms. If desired, (A) can also contain propyleneoxy groups, in which case, however, the ethyleneoxy groups preferably outweigh the propyleneoxy groups.
The polyethylene glycol monoalkyl ethers (A), which optionally contain propyleneoxy units, preferably conform to the average formula
Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)nxe2x80x94OHxe2x80x83xe2x80x83(I),
where
R is C1-4-alkyl-(O-propylene)m-,
n is from 5 to 30 and
m is from 0 to 10,
subject to the proviso that m is xe2x89xa6⅓ of n.
is preferably from 8 to 24, particularly preferably from 12 to 20.
m is advantageously xe2x89xa6xc2xc of n and is for example from 0 to 4, preferably zero.
In the first process tep (a), the oligomers (C) are first reacted with oligoethylene glycol monoalkyl ether (A), which optionally contains propyleneoxy units, the quantitative ratio of (A) to (C) being selected in such a way that only a portion of the available isocyanate groups is reacted with (A). The mixing ratio of (A) to (C) is advantageously selected in such a way that more than one mole equivalent of (C) is used per mole of (A). One equivalent of (C) is the weight, determinable by titration, which corresponds to one NCO group. One mole equivalent of (C) is this number in grams. The equivalents ratio of (A) to (C) is consequently the ratio of the number of moles of (A) to the number of mole equivalents of (C). This ratio is chiefly within the range from 1/50 to 1/2, preferably within the range of 1/40 to 1/4, particularly preferably within the range from 1/30 to 1/10.
The reaction of (A) with (C) can be carried out in the presence or absence of solvents, in which case suitable solvents are advantageously non-protogenic solvents, for example propylene carbonate, acetone, methyl ethyl ketone or methyl isobutyl ketone. When no (K) is used, the reaction is preferably carried out in the absence of solvents. The reaction takes place for example at elevated temperature, advantageously  greater than 30xc2x0 C., for example at temperatures within the range from 60 to 95xc2x0 C., and advantageously under an inert atmosphere, for example under argon or preferably nitrogen.
The reaction of (A) with (C) first gives rise to an alkyl polyglycol ether urethane product (U1), which contains urethane groups resulting from the reaction of the hydroxyl group in (A) with a portion of the isocyanate groups in (C) and preferably conforming to the formula
Rxe2x80x94(Oxe2x80x94CH2xe2x80x94CH2)nxe2x80x94Oxe2x80x94COxe2x80x94NHxe2x80x94xe2x80x83xe2x80x83(u).
Depending on the molar ratio of (A) to (C), the content of urethane components in (U1) can vary, so that the reaction product (U1), besides urethane components, can also contain unreacted components which are free of urethane groups derived from (A), i.e. fractions of (C) which have essentially not reacted with (A).
Prior to the further reaction with (B), the isocyanate-group-containing products (U1) can optionally be converted into isocyanate-group-containing products (U2) having a higher NCO-based equivalent weight.
The conversion into (U2) can advantageously be effected by inter- and/or intramolecular further reaction of (U1) or also by addition of suitable, preferably low molecular weight, chain extenders (K).
The inter- or intramolecular further reaction of (U1) can be effected by heating, for example at temperatures within the range from 60 to 95xc2x0 C., since, as the reaction time to prepare (U1) at elevated temperature is extended, the NCO-based equivalent weight will gradually rise beyond that which stoichiometrically corresponds to simple urethane formation (U1). As a result, for example, further NCO groups may be made to become involved, for example through formation of allophanate, uretidione and/or isocyanurate structures. The progress of the reaction can be monitored by determining the equivalent weight based on isocyanate groups.
Suitable chain extenders (K) for the reaction of (U1) with a chain extender (K) are generally difunctional compounds, i.e. compounds which contain at least two (e.g. 2 to 5) reactive hydrogen atoms capable of reaction with isocyanate groups, chiefly hydroxyl groups and/or primary amino groups, and which in particular do not introduce any ionic groups. Suitable (K) for the purposes of the invention include chiefly aliphatic diols, diamines or aminoalcohols which contain 2 to 6 carbon atoms and in which, if they contain 4 to 6 carbon atoms, the aliphatic radicals can optionally be interrupted by oxygen, or also especially water, water being included among the chain extenders (K) insofar as it will take part in a two-step reaction (with CO2 elimination) according to the general reaction scheme
R0xe2x80x94NCO+H2Oxe2x86x92R0xe2x80x94NH2+CO2
R0xe2x80x94NH2+OCNxe2x80x94R0xe2x86x92R0xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94R0
which leads to urea bridging. Specific examples of (K) are ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethylenediamine, tri-, tetra-, penta- or hexamethylenediamine, ethanolamine, isopropanolamine and water, of which the diols, especially ethylene glycol and propylene glycol, and particularly water are preferred.
The reaction with (K) can advantageously take place in the presence of solvents, preferably within the temperature range from 20 to 95xc2x0 C., temperatures within the range from 20 to 60xc2x0 C. being already suitable if the reaction is carried out in the presence of a catalyst of the type known for the preparation of polyurethanes, for example dibutyltin dilaurate, diacetate or dioctoate.
It is surprisingly particularly advantageous for the invention to use a reaction product (U2) in which the isocyanate-based equivalent weight has risen beyond that which stoichiometrically corresponds to simple urethane formation in reaction product (U1). The isocyanate-based equivalent weight of (U2) is advantageously by 1 to 20%, preferably 2 to 15%, more preferably 3 to 12%, higher than that which stoichiometrically corresponds to single urethane formation in (U1). The desired or optimum degree of conversion for a certain combination of starting materials (A) and (C) and optionally (K) can be determined by means of a few preliminary experiments. When a chain extender (K) is used for preparing (U2), then the ratio of the number of moles of (K) to the number of mole equivalents of (U1) is advantageously in the corresponding suitable range for achieving the aforementioned increase in the NCO-based equivalent weight, especially within the range from 0.01 to 0.16 mol of (K), advantageously 0.02 to 0.12 mol of (K), preferably 0.03 to 0.1 mol of (K), per mole equivalent of (U1).
The reaction products (U1) and (U2) are generally mixtures. The products (U1) can thus be for instance random mixtures of differingly converted products or, when, for example, the equivalents ratio of (C)/(A) is greater than the degree of oligomerization in (C), (U1) is particularly a mixture of products which contain a radical derived from (A) and products which do not contain a radical derived from (A). Corresponding further mixtures are formed in (U2).
The reaction products (U1) or preferably (U2) can then be reacted with (B).
The isocyanate-blocking pyrazoles (B) used can generally be any pyrazoles known to be useful for blocking or masking polyisocyanates, for example as described in EP-A 0500495, particularly those wherein the substituents optionally present on the pyrazole ring are non-ionogenic and also non-NCO-reactive (i.e. they do not react with NCO groups and therefore do not interfere with the blocking reaction either). As pyrazoles (B) can advantageously be employed those of the average formula 
where
R1, and R2 R3 are each, independently of the others, hydrogen, alkyl, allyl, aralkyl, aryl or alkoxy or
R2 and R3 together with the carbon atoms to which they are bonded, form a benzenic ring which is condensed to the pyrazole ring and is optionally substituted with alkyl, aryl or alkoxy.
In the formula (II), the alkyl and alkoxy groups advantageously contain 1 to 3 carbon atoms, aryl is preferably phenyl, aralkyl is preferably benzyl; when R2 and R3 together with the carbon atoms to which they are bonded form a condensed benzenic ring, this benzo ring is preferably unsubstituted. R2 is advantageously hydrogen, C1-3-alkyl, benzyl or allyl. R1 and R3 are each, independently of the other, advantageously hydrogen or C1-3-alkyl. C1-3-Alkyl is preferably methyl. R2 is particularly preferably hydrogen.
Particularly preferred pyrazoles (B) are those of the formula (II) wherein R1 is hydrogen or methyl, R2 is hydrogen and R3 is methyl.
The reaction of the pyrazoles (B) with (U1) or preferably with (U2) can be effected by simply bringing the reagents together, for example by addition of (B) into the reaction product (U1) or preferably (U2), advantageously directly after its synthesis. The blocking of the isocyanate groups with the pyrazole (B) can take place in the presence or absence of a catalyst (e.g. dibutyltin dilaurate, dioctoate or diacetate), preferably in the absence of catalysts. The reaction is exothermic, and initial gentle heating is sufficient to get the reaction going. The reaction is advantageously carried out within the temperature range from 15 to 60xc2x0 C. The amount used of pyrazole (B) is expediently sufficient to exhaustively block the isocyanate groups which are present in the employed product (U1) or (U2)xe2x80x94which may be determined by titration, for example. The reaction with (B) is advantageously also carried out under an inert atmosphere, for example under argon or preferably nitrogen, as described above for the synthesis of (U1).
The product thus prepared is a mixture (G)xe2x80x94at least to the extent that (U1) or (U2) is a mixturexe2x80x94and is essentially nonionic and self-dispersible in water, i.e. it forms very fine, aqueous dispersions by simple addition of water or by simply stirring it into water, even without the assistance of emulsifiers or other surfactants. The aqueous dispersions (D) of the mixtures (G) also form part of the subject-matter of the present invention. They are preparable in a conventional manner, by simply stirring (G) into water, or vice versa; if desired, it is also possible to add further additives, for example a non-ionogenic, surface-active stabilizer (E) and/or a solubilizer (L).
Suitable non-ionogenic stabilizers (E) are chiefly addition products of ethylene oxide to polypropylene glycol or to an aliphatic and/or aromatic alcohol having, for example, 9 to 24, preferably 11 to 18, carbon atoms, the degree of oxyethylation being advantageously such that the HLB is advantageously xe2x89xa78, preferably within the range from 10 to 18. Block polymers of ethylene oxide and propylene oxide which have the appropriate HLB are also suitable. When a non-ionogenic stabilizer (E) is used, it is advantageously used in smaller amounts than (G), for example within the range from 0.5 to 40%, preferably 1 to 20%, based on (G).
The concentration of (G) in the aqueous dispersions (D) is of itself discretionary; for concentrated dispersions (D) it is advantageously within the range from 5 to 70% by weight, preferably 10 to 60% by weight, based on total dispersion (D).
Examples of suitable solubilizers (L) are mono- or oligoalkylene glycols and their C1-4-alkyl monoethers (e.g. ethylene glycol, propylene glycol, hexylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether), ethylene carbonate, propylene carbonate or N-methylpyrrolidone.
When solubilizers (L) are used, their concentration in (D) may vary within wide limits, for example within the range from 1 to 30% by weight, based on the total weight of (D), but is advantageously inferior to the concentration of (G), for example within the range from 5 to 80% by weight of (G).
If desired, the dispersions (D) may include an additive (Z) for protection against microbial damage, especially a microbicide and/or an additive which inhibits fungal and/or bacterial growth. Suitable for this purpose are generally commercially available products, which can be used in the small amounts (e.g.  less than 2% by weight) which are recommended in each case.
The aqueous dispersions (D) of the invention are, in particular, of very fine particle size. The particle size of the dispersed particles is for example within the range from 0.01 to 1 xcexcm, preferably 0.05 to 0.5 xcexcm. The dispersions (D) are also very stable in storagexe2x80x94particularly those comprising (E) and/or (L)xe2x80x94and readily pourable. They retain their application and physical properties even after prolonged storage.
The mixtures (G) of the invention, advantageously in the form of their aqueous dispersions (D), serve as auxiliaries in the oil- and/or water-repellent finishing of fibre material with fluorocarbon polymers (F).
Suitable fluorocarbon polymers (F) are generally any of those polymers which contain perfluoro-hydrocarbon radicals (xe2x80x9cfluorocarbon radicalsxe2x80x9d) and which are known to be used for oil- and/or water-repellent finishes. The fluorocarbon radicals are chiefly perfluoroalkyl radicals, especially monovalent radicals RF of the formula
xe2x80x94CpF(2p+1)xe2x80x83xe2x80x83(f),
where p is from 3 to 21, preferably 4 to 16, or also those wherein a fluorine atom has been replaced by a chlorine atom.
These radicals RF can be linear or also branched; preferably they are linear. They are preferably radicals of the formulae 
or 
where
q is from 3 to 15, preferably 5 to 13, and
r is from 2 to 12, preferably 2 to 8.
They can for example be attached to a polymer main chain directly or via a low molecular weight aliphatic radical and optionally via an ester or ether bridge; optionally, they may also be attached to the low molecular weight aliphatic radical via an amide group. The polymer main chain is generally a hydrocarbon chain as produced by free-radical polymerization of ethylenically unsaturated monomers, for example from appropriate vinylic or (meth)acrylic monomers.
The radicals RF can for example also be attached, via a bridging member, to a nitrogen compound, for example to a condensation product of an aldehyde and a urea or melamine, chiefly to etherified methylol derivatives of urea or heterocyclic nitrogen compounds, particularly of an optionally cyclic urea (e.g. N,Nxe2x80x2-dimethylolurea, N,Nxe2x80x2-dimethylolethyleneurea, N,Nxe2x80x2-dimethylolpropyleneurea or N,Nxe2x80x2-dimethyloldihydroxyethyleneurea or a precondensate thereof) or of a methylolmelamine (e.g. tri-to hexamethylolmelamine), as condensates which are heat-curable optionally in the presence of suitable catalysts.
The fluorocarbon polymers (F) are chiefly
(FA) copolymers which contain constituent comonomer units containing fluorocarbon radicals RF or
(FB) nitrogen-containing polycondensates which contain fluorocarbon radicals RF.
Copolymers (FA) containing fluorocarbon radicals RF are well known and extensively described in the technical literature, for example in U.S. Pat. Nos. 3849521, 4742140, 5057577 and 5344903 and in EP-A 0198252 and 0294648. Polycondensates (FB) containing fluorocarbon radicals RF are likewise well known and described in the technical literature, for example in U.S. Pat. Nos. 3362782 and 3510455 and in EP-A 0073364.
It is preferred to use fluorocarbon polymers of the type (FA) for the process of the invention. They are chiefly copolymers of fluorocarbon-radicals-containing monomers (M1) of the formulae xe2x80x83RFxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x83xe2x80x83(V)
or 
where
R4 is C1-12-alkyl,
R5 is hydrogen or methyl,
R6 is hydrogen or acetyl,
X is xe2x80x94CO xe2x80x94 or xe2x80x94SO2xe2x80x94,
Y is C2-3-alkylene,
Z is C1-12-alkylene,
x is zero or 1,
y is zero or 1 and
z is zero or 1,
and further ethylenically unsaturated non-ionogenic monomers, especially
(M2) ethylenically unsaturated non-ionogenic monomers which contain lipophilic hydrocarbon radicals, for example (C9-24-alkyl) (meth)acrylates, preferably (C12-20-alkyl) (meth)acrylates,
and optionally
(M3) further non-ionogenic, ethylenically unsaturated monomers which are preferably lower in molecular weight than the first two, for example (C1-8-alkyl) (meth)acrylates (wherein alkyl radicals having 6 to 8 carbon atoms may also by cyclic), vinyl chloride, vinylidene chloride, styrene, ethylene or propylene.
If desired, (FA) may also contain minor proportions of
(M4) ethylenically unsaturated non-ionogenic comonomers which contain a reactive moiety, chiefly a reactive hydrogen attached via a heteroatom (e.g. nitrogen, sulfur or oxygen) or an epoxy group,
as polymerized units. These reactive moieties are especially moieties which, after the copolymerization of the respective monomer, are capable of crosslinking with other parts of the polymer and/or with the substrate and are, for example, hydroxyl, thiol or epoxy groups, each attached via a hydrocarbon radical, and/or a secondary amide group.
Suitable comonomers (M4) are chiefly comonomers (M4 a) of the formula
CH2xe2x95x90CR5xe2x80x94COxe2x80x94Oxe2x80x94R7xe2x80x83xe2x80x83(VII),
where
R7 is hydroxy-C2-4-alkyl, xe2x80x94(CH2xe2x80x94CH2xe2x80x94O)txe2x80x94H, dihydroxy-C3-5-alkyl, 3-chloro-2-hydroxypropyl or glycidyl and
t is from 1 to 20
or (M4b) comonomers of the formula
xe2x80x83CH2xe2x95x90CHxe2x80x94COxe2x80x94NHxe2x80x94CHR8xe2x80x94OHxe2x80x83xe2x80x83(VIII),
where R8 is hydrogen, C1-3-alkyl or xcfx89-acetyloxy-C2-4-alkyl, and their alkyl ethers, for example (C2-8-alkyl) ethers.
Preferred radicals R7 are e.g. 2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, glycidyl, 3-chloro-2-hydroxypropyl and radicals of the formula xe2x80x94(CH2xe2x80x94CH2xe2x80x94O)1xe2x80x94H, wherein t is from 1 to 10, preferably 1 to 5.
R8 is preferably hydrogen or 3-acetyloxy-2,2-dimethyl- 1-hydroxy-propyl-1.
(M1) can be a single compound or also a mixture, for example a technical grade or random mixture, for example as described in U.S. Pat. Nos. 3,849,521, 4,742,140 or 5,344,903.
Unlike the comonomers (M4), which contain a reactive moiety which, after the free-radical polymerization and after the application of the polymer to the substrate, is capable of crosslinking, the comonomers (M2) and (M3) do not contain such reactive moieties.
As (M2) can be employed one or also more compounds, for example those described in U.S. Pat. No. 5,344,903. Particular preference is given to lauryl (meth)acrylate and stearyl (meth)acrylate.
As (M3) can likewise be employed one or also more compounds, for example those described in U.S. Pat. Nos. 3,849,521 and 5,344,903 or in EP-A 0,294,648, among which C2-8-alkyl (meth)acrylates [particularly ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate], vinyl chloride and vinylidene chloride are particularly preferred.
As (M4) can also be employed one or more comonomers, for example those described in U.S. Pat. Nos. 3,849,521 and 5,344,903 or in EP-A 0,294,648, preferably at least one comonomer (M4a) and at least one comonomer (M4b).
The weight ratio of the monomers is advantageously chosen so that the resulting copolymer has the desired water- and oil-repellent effect. Based on the total quantity of the comonomers [i.e. in particular (M1) and (M2) and, if present, (M3) and/or (M4)], the comonomers (M1) are used in an amount which is advantageously within the range from 25 to 90% by weight, preferably within the range from 40 to 90% by weight, particularly preferably within the range from 40 to 75% by weight. The comonomers (M2) are used in an amount which is advantageously within the range from 5 to 50% by weight, preferably within the range from 15 to 35% by weight, based on total comonomers. The comonomers (M3) are used in an amount which is advantageously within the range from 5 to 50% by weight, preferably within the range from 5 to 25% by weight, based on total comonomers. A preferred embodiment also utilizes comonomers (M4) in minor proportions, advantageously up to 20% by weight based on total comonomers. The amount of (M4) employed is preferably 0.1 to 20% by weight, particularly preferably 2 to 15% by weight, for example 0.2 to 5% by weight of (M4a) and 1.5 to 12% by weight of (M4b). The copolymerization can take place in a manner conventional per se, advantageously in aqueous emulsion in the presence of suitable emulsifiers and optionally solubilizers. Any suitable emulsifiers can be used, especially non-ionogenic and/or cationic emulsifiers. Examples of suitable non-ionogenic emulsifiers are addition products of ethylene oxide with higher fatty alcohols (e.g. with 9 to 24 carbon atoms in the fatty radical) or with fatty acid partial esters of oligoalkanols such as glycerol, sorbitol or sorbitan wherein the fatty acid radicals advantageously contain 12 to 24 carbon atoms. The HLB value of the non-ionogenic surfactants is advantageously xe2x89xa710, preferably within the range from 12 to 18. Examples of cationic surfactants are simple fatty amines having, for examples, 12 to 24 carbon atoms in the fatty radical, or protonation or quaternization products thereof. Small amounts of the emulsifiers are sufficient for the polymerization in aqueous emulsion, for example 1 to 20% by weight, preferably 2 to 15% by weight, based on the total monomers or respectively on (F).
When solubilizers are used, their concentrations are advantageously within the range from 5 to 50% by weight based on total monomers or on (F). Examples of suitable solubilizers are customary compounds as mentioned above as (L), for example mono- or oligoalkylene glycols and their lower alkyl ethers. If desired or required, other customary additives are used for the polymerization, for example polymerization regulators and/or catalysts.
The polymerization advantageously takes place at elevated temperature, for example within the temperature range from 40 to 90xc2x0 C., advantageously under an inert atmosphere, for example under nitrogen. The amount of water for the emulsion polymerization is advantageously chosen so that an (F)-dispersion of the desired concentration is produced, for example of a concentration within the range from 5 to 50% by weight, advantageously 10 to 40% by weight, preferably 15 to 30% by weight. The desired emulsion form can expediently also be obtained by suitable stirring.
The mixtures (G) of the invention serve as additives for improving the oil- and water-repellent effect of (F)-finishes and their fastnesses, especially fastnesses to cleaning. Suitable substrates for the finish of the invention include any materials known to be given an oil- and water-repellent finish with fluoro-carbon polymers, for example fibrous materials composed of natural, semisynthetic or fully synthetic materials, especially optionally modified cellulose (e.g. cotton, hemp, jute, viscose rayon, cellulose acetates) and blends thereof with synthetic fibres (especially cotton/polyester, cotton/polyamide, cotton/polyurethane, cotton/viscose, cotton/polyester/polyurethane), and synthetic fibres (e.g. polyamide, polyester, polyacrylonitrile). The fibrous materials can be present in any desired suitable processing form used for finishing with fluorocarbon polymers, especially as wovens, knits, carpets, felts, webs and nonwovens, or else textiles coated with a polymeric film as are used for example for manufacturing weatherproof products (raincoats, anoraks, windcheaters, tents, tarpaulins, etc.), or products which are cleaned by shampooing (e.g. carpets, upholstery covers). The finishing can be carried out before or also after the making up.
The mixtures (G) of the invention are advantageously applied together with (F) to the substrate to be finished; for this purpose, it is possible to combine them, advantageously in the form of their aqueous dispersions (D), with (F) in a suitable treatment liquor, or (D) can for example be formulated beforehand with (F) to form a stock liquor, or (D) can be formulated with a polymer (F) during or after the synthesis of (F) into an aqueous, concentrated composition. The polymers (F) are advantageously employeded in the form of aqueous dispersions (which may include conventional additives, such as emulsifiers or solubilizers) whose concentration of (F) is for example within the range from 5 to 50% by weight, preferably 10 to 40% by weight. The aqueous compositions (P) comprising (G) and (F), especially the concentrated compositions (P1), the prediluted compositions (P2) (especially stock liquors) and the diluted compositions (P3) (particularly treatment liquors), likewise form part of the subject-matter of the present invention. These compositions, especially (P1), advantageously comprise at least one component (L) and/or (Z) which may each derive for example from the production of a corresponding (F)-dispersion and/or from the production of (D), or may also be added separately.
The weight ratio of (G) to (F) is advantageously chosen so that a marked improvement in the effect of (F) in the finish is brought about. The weight ratio of (G)/(F) is advantageously within the range from 5/100 to 120/100, preferably 10/100 to 90/100, particularly preferably 20/100 to 70/100.
The concentration of [(G) +(F)] in the aqueous compositions (P) can vary within wide limits, for example within the range from 0.1 to 70% by weight.
The concentration of [(G) +(F)] in the concentrated, aqueous compositions (P1) comprising (G) and (F) is for example within the range from 10 to 70% by weight, preferably from 15 to 50% by weight, based on the total composition (P1). In the prediluted, aqueous compositions (P2) comprising (G) and (F), the concentration of [(G) +(F)] is for example within the range from 0.3 to 30% by weight, preferably 1.5 to 15% by weight, based on the total composition (P2). In the aqueous treatment liquors comprising (G) and (F), i.e. in the compositions (P3), the concentration of [(G) +(F)] is for example from 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total composition (P3).
If desired, the finish may be combined with another customary synthetic resin finish, for example a synthetic resin finish based on optionally cyclic methylolureas or methylolmelamines or also precondensates thereof, for example as described above as precursors for the production of (FB). If the finishing is carried out in the presence of synthetic resin, the corresponding synthetic resin precursor and any catalyst which may be required may also be present in (P3).
The pH of the treatment liquor can vary within wide limits, for example within the range from 2.5 to 8, preferably 4 to 7.5, in which the corresponding suitable or optimal pH can be chosen according to the selected finish combination.
The finishing can be effected in a manner conventional per se, chiefly by means of impregnation processes, for example by padding, by dipping, by spraying, by knife-coating or by curtain coating, and similar continuous or discontinuous processes. The presence of the additive (G) or respectively (D) according to the invention makes it possible to reduce the amount of polymer (F) required, especially the requisite minimum or optimum amount to obtain effective results, to a substantial extent. The concentration of (F) based on the dry substrate is for example within the range from 0.1 to 5%, preferably 0.2 to 3%, by weight. The application of the treatment liquor to the substrate can be followed by a suitable thermofixation as required for the respective polymers (F) and optionally synthetic resin, for example within the temperature range from 110 to 220xc2x0 C., preferably 120 to 200xc2x0 C., for example for 10 seconds to 2 minutes, an optimal fixation temperature and time being choosable as a function of the type and consistency of the substrate, the presence or absence of synthetic resin, and the composition and concentration of the liquor. The thermofixation is advantageously preceded by predrying, for example within the temperature range from 100 to 140xc2x0 C., for example for 30 seconds to 5 minutes.
The presence of the additive (G) or respectively (D) of the invention makes it possible to enhance the effect of the (F) finish and improve its fastnesses, or respectively to substantially reduce the amount of polymer (F) required for achieving a certain effect level. This means that (G), preferably in the form of (D), can be used as an effective extender or blending agent for (F), so that a minimal amount of fluorocarbon polymer (F) can be used to obtain optimal oil- and water-repellent finishes which, moreover, have noteworthy fastnesses, especially fastnesses to cleaning (chiefly fastnesses to shampooing and washing), while the specific properties are practically unimpaired or may even be improved. Owing to the particularly good fastnesses to cleaning, it is additionally also possible for the finished materials to be for example washed in a domestic washing machine (e.g. windcheaters or raincoats and the like) and air dried or also tumble dried, or to be shampooed (e.g. carpets, upholstery covers and the like) and air dried, without a subsequent heat treatment, for example ironing, being absolutely necessary.
In the Examples hereinbelow, parts and percentages are by weight and the temperatures are reported in degrees Celsius.